The aim of this thesis was to modify microstructure and coating-substrate interface of CoNiCrAlY coatings deposited by HVOF and cold spray on Inconel 718 substrates. Electron beam remelting and annealing in a protective atmosphere were used to modify the coatings. Microstructure, chemical and phase composition were analyzed. The effect of beam current, transversal velocity and beam defocus on remelted depth was evaluated. As-sprayed microstructure and chemical composition of coatings were analyzed and compared with remelted samples. The effect of annealing of the as-sprayed and remelted samples was evaluated. Remelted layers exhibited dendritic structure. Chemical composition changed only after remelting of interface and part of a substrate. When only the coating was remelted, chemical composition remained the same. Phases coarsened after the annealing. Chemical composition changed after annealing due to the diffusion.

A liga Ti-6Al-4V tem sido usada com sucesso como biomaterial com aplicações nos campos da odontologia e ortopedia. As características da liga Ti-6Al-4V que a tornaram um material interessante são sua boa resistência à corrosão em meio biológico, combinada com um excelente grau de biocompatibilidade. Os efeitos biológicos a longo prazo dos íons metálicos resultantes da lenta lixiviação dos implantes de titânio não estão completamente entendidos. É conhecido que os íons titânio são considerados agentes químicos cancerígenos, os íons alumínio causam desordem neurológicas e os íons vanádio estão associados com distúrbios enzimáticos, entre outros problemas. O recobrimento das ligas de titânio por óxido de titânio (TiO2) pode atuar como uma barreira química para os íons lixiviados da superfície metálica da liga, além deste óxido ser um bom osseoindutor. O processo de aspersão térmica é amplamente empregado na aplicação de recobrimentos por óxidos. Uma vez que este processo acontece em altas temperaturas, onde partículas fundidas ou semi-fundidas aderem ao substrato, pode ocorrer difusão localizada. O objetivo deste estudo é caracterizar a interdifusão dos elementos de liga através das camadas superficiais do sistema Ti-6Al-4V/TiO2. Os recobrimentos de TiO2 foram preparados pela técnica de aspersão por plasma. A zona recoberta mostrou pequena porosidade distribuída por toda a camada e algumas trincas radiais. Adicionalmente, uma grande quantidade de buracos foi observada na região entre-camadas. Neste trabalho, a interface Ti-6Al-4V/TiO2 foi estudada por microscopia eletrônica de varredura. Os perfis de difusão do Ti, Al, V e O nas camadas superficiais da amostra recoberta foram obtidos por microanálise semi-quantitativa por energia dispersiva de raios-X. A caracterização química superficial do lado substrato depois da deposição de TiO2 mostrou a formação localizada de TiO. Na região entre-camadas foram observados os perfis de difusão característicos com forma de S para o Ti, V e O. O perfil de difusão do Al mostrou um pico na região entre-camadas indicando um acúmulo de Al2O3 nos buracos presentes nesta zona. O TiO2 foi identificado como o maior constituinte no lado revestimento. Pequenas quantidades de Al e V foram também detectadas homogeneamente distribuídas dentro do depósito. A presença do Al e V (metais tóxicos) na superfície externa do depósito indica que estes metais não competem com a oxidação da camada depositada indicando um efeito desmascarante da superfície da liga metálica pelo óxido superficial TiO2. / Ti-6Al-4V alloy has been used with some success as biomaterial with applications in the field of dentistry and orthopaedics. The features with make the Ti-6Al-4V alloy such an interesting material are its good corrosion resistance in the biological environment, combined with an excellent degree of biocompatibility. The long-term biological effects of the slowly leaching of metal ions from titanium implants are not completely understood. It is known that the titanium ions are considered chemical carcinogen, aluminium ions cause neurological disorders and, vanadium ions are associated with irreversible enzymatic disturbance, among other problems. Titanium oxide (TiO2) coatings on titanium alloys can act as a chemical barrier for ions leaching from the metallic alloy surface, beside the fact that this oxide is a very good osteoinductor. The thermal spray process is widely used to apply oxide coatings. Once this is a high temperature process where molten or semi-molten particles impinge upon the substrate, localized diffusion can occur. The aim of this study is characterize the inter-diffusion of the alloying elements through the surface layers of the system Ti-6Al-4V/TiO2. The TiO2 coatings were prepared by the plasma spray technique. The coated zone showed some porous distributed in all layer and a few radial cracks. Additionally, large amount of holes were observed in the interlayer region. In this work, the interface Ti-6Al-4V/TiO2 was studied by scanning electron microscopy. Diffusion profiles of Ti, Al, V and O in the surface layers of coated samples were measured by semi-quantitative energy dispersive X-ray microanalysis. Chemical surface characterization of the substrate side after the TiO2 deposition showed the localized formation of TiO. At the interlayer region was observed the characteristic S shape diffusion profiles for Ti, V and O. The Al diffusion profile showed a peak in the interlayer region indicating anaccumulation of Al2O3 into the holes present in this zone. TiO2 was identified as the major component in the coating side. Small amounts of Al and V were also detected homogeneously distributed inside the deposit. Presence of Al and V (toxic metals) on the external surface of the deposit indicated that these metals did not compete with the oxidation of the deposited layer indicating a non-masking effect of metallic alloy surface by the TiO2- surface oxide.

Due to their ability to confer enhanced surface properties without compromising the properties of the substrate, coatings have become ubiquitous in heavy industrial applications for corrosion, wear, and thermal protection, among others. Kinetic Metallization (KM), a solid-state impact consolidation and coating process, is well-suited for depositing industrial coatings due to its versatility, low substrate heat input, and low cost. The ability of KM coatings to adhere to the substrate is determined by the quality of the interface. The purpose of this study is to develop a model to predict the interfacial quality of KM coatings using known coating and substrate properties. Of the various contributions to adhesion of KM coatings, research suggests that the thermodynamic Work of Adhesion (WAD) is the most fundamental. It is useful to define interfacial quality in terms of the critical strain energy release rate (GC) at which coating delamination occurs. Studies show that GC for a given interface is related to WAD. This study attempts to develop a theoretical model for calculating WAD and understand the relationship between GC and WAD. For a bimetallic interface between two transition metals, WAD can be theoretically calculated using known electronic and physical properties of each metal: the molar volume, V, the surface energy, γ, and the enthalpy of alloy formation, ΔHinterface; ΔHinterface is a function of the molar volume, V, the work function, φ, and the electron density at the boundary of the Wigner-Seitz cell, nWS.WAD for Ni-Cu and Ni-Ti interfaces were 3.51 J/m2 and 4.55 J/m2, respectively. A modified Four-point bend testing technique was used to experimentally measure GC for Ni-Cu and Ni-Ti specimens produced by KM. These tests yielded mean G­C values of 50.92 J/m2 and 132.68 J/m2 for Ni-Cu and Ni-Ti specimens, respectively. Plastic deformation and surface roughness are likely the main reasons for the large discrepancy between GC and WAD. At the 95% confidence level, the mean GC of the Ni-Ti interface is significantly higher than that of the Ni-Cu interface. Further testing is recommended to better understand the relationship between WAD and GC.

Ce mémoire présente la modélisation, la simulation, l’expérimentation et la conception d’une structure composite intelligente pour des mesures de haute température (jusqu’à 300 °C). Pour ce faire, une fibre à revêtement métallique, particulièrement résistante pour de tels niveaux thermiques, a été considérée et intégrée au sein d’un revêtement d'alumine. La structure composite intelligente se compose alors du substrat, du dépôt et d’un capteur à fibre optique à modulation d’intensité. Pour mener cette étude, une estimation des flux thermiques basée sur le thermogramme expérimental s’est révélée nécessaire afin d’alimenter un modèle numérique. Différents modèles ont ensuite été construits afin d’évaluer les niveaux de températures atteints en surface ainsi que les niveaux de contraintes au sein même du composite. La simulation a montré que le dépôt pouvait thermiquement être considéré comme une couche mince et que la diffusion de la chaleur au sein du dépôt et du substrat était rapide et pouvait être estimée à l'échelle de la milliseconde. La répartition des contraintes est comme on pouvait s'y attendre dépendante du flux incident mais aussi de la géométrie globale du composite. Les contraintes restent relativement uniformes lors de l'échauffement et durant leur propagation mais s’intensifient après le refroidissement. Il s'avère également que les contraintes résultantes ne sont pas symétriques dans la fibre et sont dépendantes de la position de la fibre par rapport au substrat. Après une phase de modélisation des niveaux thermiques et des contraintes susceptibles d’être atteints au sein du matériau, une phase expérimentale consistant à intégrer une fibre optique non fonctionnalisée dans un dépôt d’alumine a donc été réalisée. Les observations microscopiques en surface et en coupe ont été effectuées afin de vérifier l’intégrité de la fibre intégrée. L’adhérence mécanique des fibres a ensuite été mesurée ainsi que l’atténuation optique pendant le processus d’intégration et le comportement thermique de l’ensemble durant des cyclages thermiques. Enfin, un capteur à fibre optique à modulation d’intensité a été conçu par intégration dans un dépôt céramique réalisé par projection thermique. Un système de mesure de la température a donc été construit et les premiers essais de réponse thermique ainsi que le cyclage thermique du capteur de température ont été effectués et analysés. En concluision, cette étude démontre la faisabilité d’une structure composite intelligente par intégration d'un capteur à modulation d’intensité à fibre optique dans un dépôt céramique élaboré par projection thermique susceptible de pouvoir travailler jusqu’à des températures de 300 °C. / This paper presents the modeling, simulation, experimentation and design of a smart composite structrure for high temperature measurements (up to 300 °C). In order to achieve this goal, a high temperature resistant metal coated optical fiber was considered and integrated into alumina coating. The smart composite structure consists of a substrate, a coating and an intensity modulated optical fiber temperature sensor. Firstly, an estimation of heat flux based on a experimental thermogram was firstly carried out in order to feed a numerical modeling. Then, different modelings were built to evaluate the surface temperature levels as well as the composite stress levels. The simulation showed that the composite (substrate and coating) could be considered as a thermally thin medium, the heat propagation within the composite was fast and could be estimated at a scale of millisecond. The stresses remained relatively uniform during the heating process but intensified during the cooling process. The modeling also showed that the stresses are not symmetrical in the fiber and depend on the position of the fiber relative to the substrate. After a modeling evaluation of the thermal levels as well as the stresses that may be achieved in the composite, an experimental step integrating a optical fiber into a thermal coating was carried out. Microscopic observation of surface and cross section were conducted in order to analyze the characteristics of the integrated fiber. The mechanical strength of the integrated fiber was then measured and the optical attenuation during the integration process as well as the thermal behavior of the integrated fiber during the thermal cycling were evaluated. Finally, an intensity modulated optical fiber temperature sensor was designed and integrated into ceramic coating by thermal spraying. A temperature measuring system was designed and the first tests of the thermal response as well as thermal cycling of temperature sensor were carried out. This study demonstrates the feasibility of designing a high temperature resistant smart composite structure by integrating an intensity modulated optical fiber temperature sensor in a ceramic coating elaborated by thermal spraying.

L'adhésion des revêtements est l'objectif premier de tout système afin de pouvoir apporter les propriétés de surface voulues par projection thermique. De façon conventionnelle, des traitements de sablage sont régulièrement employés afin de promouvoir des phénomènes d'ancrage mécanique entre les deux matériaux mis en contact.Néanmoins, selon la nature même des matériaux, un certain nombre de limitations peuvent être observées aussi bien d'un point de vue usage que tenue. Une fragilisation des surfaces peut en effet être remarquée dès lors qu'ils'agit du traitement de matériaux ductiles. Pour palier certaines de ces contraintes, des traitements palliatifs sont alors recherchés parmi lesquels les traitements laser apparaissent particulièrement bénéfiques dont la texturation laser. Les revêtements barrière thermique sont l'application visée de cette étude avec comme objectif une optimisation de leur durabilité à chaud (oxydation, fluage). Une sous-couche d'accroche est habituellement déposée mais les modes d'endommagement recensés semblent se concentrer autour de cette dernière. L'objectif de c etravail a donc visé à remplacer la sous-couche par une topographie de surface spécifique du substrat générée partexturation laser et permettant un ancrage mécanique suffisant aux chargement mécaniques et thermiques subis par les aubes de turbines hautes températures.Lors de l'interaction laser-matière, une élévation en température de l'extrême surface jusqu'à la température defusion et de vaporisation du matériau peut être observée et permettre la formation de motifs. Les dimensions de tels motifs sont donc liées à l¿énergie par impulsion et au nombre d¿impulsions. Pour valider de tels effets, les mécanismes de perçage ont donc été étudiés grâce à une modélisation thermo hydraulique et une validation postmortem des échantillons. Les dimensions des motifs alors contrôlées, le remplissage des surfaces texturées par des particules fondues projetées par le procédé APS a été étudié afin de minimiser le nombre de défauts proche de l'interface. Deux modes de rupture ont pu être identifiés en fonction de la morphologie de surface pour descontraintes de traction et de cisaillement. Les fissures se propagent à l'interface jusqu'à avoir des changements dedirection. L'énergie de propagation de la fissure augmente donc jusqu'à atteindre une valeur limite correspondant àla ténacité du revêtement. Dans ce cas, la tenue n'est pas fonction de la surface totale en contact mais de larépartition spatiale et l'ouverture des motifs, la seule limite de la tenue du revêtement restant la cohésion du dépôt.D'un point de vue applicatif, le but de cette étude a été de caractériser les modes d'endommagements de systèmes barrière thermique sans sous-couche pour des conditions rencontrées en service. Les mécanismes d'endommagement dus à l'oxydation et à l'allongement viscoplastique à 1100C ont donc été isolés par des essais àdes flux thermiques isothermes et cyclés, de fluage et de fatigue thermomécanique. Le traitement laser modifiant localement la microstructure des surfaces, une modification des couches d'oxydes a tout d'abord pu être identifiée.En effet, contrairement aux traitements conventionnels où la croissance d'oxyde n'est pas constante (point limitant de la durée de vie du système), l'apparition de spinelles et d'une couche dense d'alumine protectrice en surface des matériaux texturés a pu être observée. L'ancrage mécanique ainsi créé a démontré alors une durée de vie nettement améliorée face à des conditions extrêmes. / Coating adhesion is requiered to rpomote specific surface properties by thermal spraying. Conventional prior-surface treatments have been developed to create anchoring zones but the adhesion strenght and their applications are limited. Laser surface texturing increases and adapts the adhesion surface. Therefore, two interface failure modes have been related to texture morphologies for tensile and shear stresses. The energy released rate at the interface increases up to coating toughness when the crack path is sharp. Mixed-mode failures have been observed with adhesive and cohesive cracks around and above pattern respectively. So, the adhesion stengyh is function of the contact aera precisely linked to pattern distribution and morphology. Thermal barrier coating system without bond coat life-span has been evaluated for thermomechanical stresses (YSZ coating on single crystal based Nickel). The bond coat has been remplaced by an adapted substrate surface topography. According ti the laser parameters (energy per pulse, pulse numbers) pattern morphology can be created. Therefore, textured surface filling by melted particles has been studies to minimize interface defaults and created mixed-mode failures for during plasma spray coatings. The drilling mechanisms have been evaluated by numerical modeling and experimental analysis. The pattern dimensions and heat affected zones has been identified. The laser treatment changes the microstructure locally.Oxydation tests have been performed to study the surface pre-tratments effects on oxide nature and mass gain rate. The damaging mechanisms ave been studied under isotherm and cyclic high temperature tests and also under creeping and thermo-mechanical fatigue tests. Grit-blasting change the natural oxides, limits life-span and bucking failure mode have been obeserved. Natural oxides have been analyzed for the textured substraes also but anchoring mechanism enables large life-span under high temperature tests. Mechanical applied stresses (constant and cyclic) validate the beneficial effects of patterned surfaces. The interface is stronger than the coating toughness and the patterns do not create early cracks under thermo-mechanical solicitations.

Thermal spray coatings applied with high velocity techniques produce dense, industrial quality coatings with strong adhesion and minimal decomposition. This thesis reports on investigations of splat-substrate interactions for both solid and molten splats. Specifically, individual particles were studied to see how the particle is altered during the spray coating process, how they bond to the substrate and the role of surface oxides. Investigations of NiCr particles high velocity air fuel (HVAF) thermally sprayed onto different materials found that soft substrates predominantly had deeply penetrating solid particles, whereas harder substrates resisted particle penetration and had a higher percentage of molten splats. This effect is caused by particle kinetic energy converted into heat during plastic deformation. The percentage of particle kinetic energy converted into heat is proportional to substrate hardness. It was also discovered that during the coating process the oxide is not removed or altered in composition, but becomes redistributed over a larger surface area due to the plastic deformation of the substrate. During this process, small scale redistribution and penetration of the oxide material by the incoming particle occurs. These results support the idea that successful bonding can occur only when the surface oxide on the substrate and on the coating material has been disturbed (for solid splats) or disrupted (for molten splats). To date, our knowledge of solid splat bonding processes within thermal spray coatings has been very subjective where mechanical and chemical bonding has been expected to contribute. In this thesis, the splat-substrate interface was investigated with focused ion beam (FIB) microscopy, cross-sectional SEM and cross-sectional TEM. For solid NiCr splat HVAF coatings, the discovery of interfacial formations, together with no evidence of chemical bonding across the particle-substrate interface suggest that mechanical bonding is the dominant bonding mechanism for solid splat coatings; where as chemical bonding only plays a role when splats and/or substrate become molten. / GNS Science

Thermal spray coatings applied with high velocity techniques produce dense, industrial quality coatings with strong adhesion and minimal decomposition. This thesis reports on investigations of splat-substrate interactions for both solid and molten splats. Specifically, individual particles were studied to see how the particle is altered during the spray coating process, how they bond to the substrate and the role of surface oxides. Investigations of NiCr particles high velocity air fuel (HVAF) thermally sprayed onto different materials found that soft substrates predominantly had deeply penetrating solid particles, whereas harder substrates resisted particle penetration and had a higher percentage of molten splats. This effect is caused by particle kinetic energy converted into heat during plastic deformation. The percentage of particle kinetic energy converted into heat is proportional to substrate hardness. It was also discovered that during the coating process the oxide is not removed or altered in composition, but becomes redistributed over a larger surface area due to the plastic deformation of the substrate. During this process, small scale redistribution and penetration of the oxide material by the incoming particle occurs. These results support the idea that successful bonding can occur only when the surface oxide on the substrate and on the coating material has been disturbed (for solid splats) or disrupted (for molten splats). To date, our knowledge of solid splat bonding processes within thermal spray coatings has been very subjective where mechanical and chemical bonding has been expected to contribute. In this thesis, the splat-substrate interface was investigated with focused ion beam (FIB) microscopy, cross-sectional SEM and cross-sectional TEM. For solid NiCr splat HVAF coatings, the discovery of interfacial formations, together with no evidence of chemical bonding across the particle-substrate interface suggest that mechanical bonding is the dominant bonding mechanism for solid splat coatings; where as chemical bonding only plays a role when splats and/or substrate become molten. / GNS Science

Thermal spray coatings applied with high velocity techniques produce dense, industrial quality coatings with strong adhesion and minimal decomposition. This thesis reports on investigations of splat-substrate interactions for both solid and molten splats. Specifically, individual particles were studied to see how the particle is altered during the spray coating process, how they bond to the substrate and the role of surface oxides. Investigations of NiCr particles high velocity air fuel (HVAF) thermally sprayed onto different materials found that soft substrates predominantly had deeply penetrating solid particles, whereas harder substrates resisted particle penetration and had a higher percentage of molten splats. This effect is caused by particle kinetic energy converted into heat during plastic deformation. The percentage of particle kinetic energy converted into heat is proportional to substrate hardness. It was also discovered that during the coating process the oxide is not removed or altered in composition, but becomes redistributed over a larger surface area due to the plastic deformation of the substrate. During this process, small scale redistribution and penetration of the oxide material by the incoming particle occurs. These results support the idea that successful bonding can occur only when the surface oxide on the substrate and on the coating material has been disturbed (for solid splats) or disrupted (for molten splats). To date, our knowledge of solid splat bonding processes within thermal spray coatings has been very subjective where mechanical and chemical bonding has been expected to contribute. In this thesis, the splat-substrate interface was investigated with focused ion beam (FIB) microscopy, cross-sectional SEM and cross-sectional TEM. For solid NiCr splat HVAF coatings, the discovery of interfacial formations, together with no evidence of chemical bonding across the particle-substrate interface suggest that mechanical bonding is the dominant bonding mechanism for solid splat coatings; where as chemical bonding only plays a role when splats and/or substrate become molten. / GNS Science

Thermal spray coatings applied with high velocity techniques produce dense, industrial quality coatings with strong adhesion and minimal decomposition. This thesis reports on investigations of splat-substrate interactions for both solid and molten splats. Specifically, individual particles were studied to see how the particle is altered during the spray coating process, how they bond to the substrate and the role of surface oxides. Investigations of NiCr particles high velocity air fuel (HVAF) thermally sprayed onto different materials found that soft substrates predominantly had deeply penetrating solid particles, whereas harder substrates resisted particle penetration and had a higher percentage of molten splats. This effect is caused by particle kinetic energy converted into heat during plastic deformation. The percentage of particle kinetic energy converted into heat is proportional to substrate hardness. It was also discovered that during the coating process the oxide is not removed or altered in composition, but becomes redistributed over a larger surface area due to the plastic deformation of the substrate. During this process, small scale redistribution and penetration of the oxide material by the incoming particle occurs. These results support the idea that successful bonding can occur only when the surface oxide on the substrate and on the coating material has been disturbed (for solid splats) or disrupted (for molten splats). To date, our knowledge of solid splat bonding processes within thermal spray coatings has been very subjective where mechanical and chemical bonding has been expected to contribute. In this thesis, the splat-substrate interface was investigated with focused ion beam (FIB) microscopy, cross-sectional SEM and cross-sectional TEM. For solid NiCr splat HVAF coatings, the discovery of interfacial formations, together with no evidence of chemical bonding across the particle-substrate interface suggest that mechanical bonding is the dominant bonding mechanism for solid splat coatings; where as chemical bonding only plays a role when splats and/or substrate become molten. / GNS Science

Beim Flammspritzen von Mischungen im System Al2O3-TiO2-ZrO2 treten vielfältige Effekte auf. Es kommt z.B. zur Ausbildung eines amorphen Anteils, der in Form von amorphen Sublamellen, dem primären amorphen Anteil, und in dendritisch geprägten Bereichen, dem sekundären amorphen Anteil im Gefüge vorliegt. Dieser beeinflusst die mechanischen Eigenschaften deutlich. Bei einer Temperaturbehandlung entstehende Ausscheidungen von ZrO2 oder verschiedenen Zirkoniumtitanaten beeinflussen die mechanischen Eigenschaften ebenfalls signifikant.